AZO Dyes from 2-sulfonated, sulfated or thiosulfated organothiothiadiazole and aniline, tetrahydroquinoline, or benzomorpholine couplers

ABSTRACT

Disclosed are azo dyes having the general formula ##STR1## in which A is the residue of an aniline, tetrahydroquinoline or benzomorpholine disperse dye coupling component, R is a divalent organic radical such as straight or branched, lower or cyclic aliphatic or arylene, each of which may be substituted, Z is SO 3 , SO 4  or SSO 3 , and M is hydrogen, an alkali metal or ammonium. These dyes produce orange to bluish red shades and exhibit one or more improved properties such as dyeability, light fastness, blooming, pH stability, build, and the like on, for example, polyamide, wool, and cellulose ester fibers.

This is a continuation-in-part application of Ser. No. 174,055, filed July 31, 1980, now abandoned.

This invention concerns azo dyes having the general formula ##STR2## in which A is the residue of an aniline, tetrahydroquinoline or benzomorpholine disperse dye coupling component, R is a divalent organic radical such as lower straight, lower branched or cyclic aliphatic or arylene or combination thereof, each of which may be substituted and selected for example from ##STR3## an alkali metal or ammonium. Substituents pendant from or within the chain of the R groups include ##STR4## and the like. These dyes produce red to bluish red shades and exhibit one or more improved properties such as dyeability, dye exhaustion rate, light fastness, blooming, pH stability, build, crock, wash, ozone and nitrogen oxide fastness and the like on, for example, polyamide, wool, and cellulose ester fibers.

The couplers useful in the present invention have the formulae ##STR5## wherein R⁶ and R⁷ are each selected from hydrogen, fluorine, chlorine, bromine, lower alkyl, cycloalkyl, lower alkoxy, phenoxy, lower alkylthio, arylthio, and radicals having the formula --NH--X--R¹³ in which X is --CO--, --COO--, or --SO₂ -- and R¹³ is selected from aryl, cycloalkyl, lower alkyl and lower alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, lower alkylsulfonyl, lower alkylthio, lower alkanoyloxy, and lower alkoxy, and when X is --CO--, R¹³ also can be hydrogen, amino, lower alkylamino, lower alkylcarbamoyl, lower dialkylamino, arylamino, or furyl;

R⁸ and R⁹ are selected from hydrogen; cycloalkyl; cycloalkyl substituted with one or two groups selected from lower alkyl; --OH, lower alkoxy, halogen and hydroxy substituted lower alkyl; phenyl or phenyl substituted with lower alkyl, lower alkoxy, halogen, lower alkanoylamino, cyano or lower alkoxycarbonyl; straight or branched lower alkenyl, straight or branched alkyl of 1-8 carbons and such alkyl substituted with the following: hydroxy; halogen; cyano; succinimido; glutarimido; phthalimido; 2-pyrrolidono; cyclohexyl; phenyl or phenyl substituted with 1-3 of lower alkyl, halogen, cyano, sulfamoyl, OH, OR¹³, OXR¹³, SR¹³, XR¹³, NHXR¹³, ##STR6## SO₂ NHR¹³, O(CH₂)_(n) XR¹³, O(CH₂)_(n) OR¹³, where n is 1-6; lower alkylsulfamoyl; vinylsulfonyl; acrylamido; phthalimidinyl; benzoylsulfonicimidyl; lower alkylsulfonamido; phenylsulfonamido; lower alkoxycarbonylamino; lower alkylcarbamoyloxy; lower alkoxycarbonyl; lower alkoxycarbonyloxy; groups of the formula ##STR7## wherein Y is --NH--, --NH--lower alkyl--, --O--, --S--, or --CH₂ O--; --S--R¹⁴ wherein R¹⁴ is lower alkyl, phenyl, phenyl substituted with halogen, lower alkyl, lower alkoxy, lower alkanoylamino, cyano, or lower alkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, triazolyl, or ##STR8## --SO₂ R¹³ ; --COOR¹³ ; --OXR¹³ ; --NH--X--R¹³ ; --X--R¹³ ; --OCO--R¹³ ; --CONR¹⁵ R¹⁵ ; --SO₂ NR¹⁵ R¹⁵ ; wherein R¹³ and X are as defined above and each R¹⁵ is selected from H and R¹³ ; lower alkoxy; lower alkoxy substituted with hydroxy, cyano, lower alkanoyloxy, or lower alkoxy; phenoxy; phenoxy substituted with one or more of lower alkyl, lower alkoxy or halogen; and R⁸ and R⁹ can be a single, combined group which, with the nitrogen atom to which each is attached, forms a ring such as pentamethylene, ethyleneoxyethylene and ethylenesulfonylethylene;

R¹⁰, R¹¹ and R¹² are each selected from hydrogen and lower alkyl; and R¹⁶ is selected from hydrogen, lower alkyl, --OH, --Cl, --CONH₂, --CONH--lower alkyl, lower alkoxy, phenoxy, --SR¹⁴, and --OXR¹³ wherein R¹³ and R¹⁴ are as defined above. The term "lower" as used herein means 1-6 carbons.

The couplers are prepared by procedures well known in the art and such couplers are disclosed in general in the patent literature, e.g., U.S. Pat. Nos. 2,805,218; 2,827,450; and 2,839,523.

The azo moieties are prepared by procedures known to the art as exemplified below.

GENERAL PREPARATIVE METHODS

1. Diazotization and Coupling--The intermediate 2-amino-1,3,4-thiadiazoles III may be prepared by reacting 2-amino-5-mercapto-1,3,4-thiadiazole (I) with appropriate halides II as follows: ##STR9## Compounds III are then diazotized and coupled in the normal manner to give dyes IV ##STR10##

2. Reaction With Sulfite and Thiosulfate Salts--Compounds (V) contaning halogens such as Cl, Br and I can be reacted with sulfites or thiosulfates to give VI and VIII, respectively as follows: ##STR11##

3. Reaction of Hydroxyl Containing Dye With Sulfuric Acid--Sulfate esters (IX) may be prepared by reacting dyes VIII containing one or more hydroxyl groups with sulfuric acid as follows: ##STR12## Salts X of the sulfate esters are prepared by neutralizing IX with base, such as alkali metal hydroxides, metal carbonates or ammonium hydroxide as shown above.

4. Direct Sulfonation--When R contains an aromatic ring, with or without a linking group R₁, the sulfonic acid derivatives may be prepared by direct sulfonation, either to produce dyes XI directly or intermediate XII may be sulfonated, followed by diazotization and coupling, to give dyes XI as follows: ##STR13##

This invention with be further illustrated by the following examples although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention.

EXAMPLE 1 Preparation of 2-Amino-5-[(2-Sulfoethyl)Thio]-1,3,4-thiadiazole Na Salt

2-Amino-5-mercapto-1,3,4-thiadiazole (13.3 8, 0.10 m), 2-bromoethanesulfonic acid, Na salt (21.1 g, 0.10 m), sodium carbonate (0.11 m), sodium iodide (1 g), and water (100 ml) are heated on a steambath until reaction is complete as determined by thin-layer chromatography, usually within 6 hours. The reaction mixture is cooled and drowned into about 500 ml of acetone. The white precipitate is collected by filtration and dried in air. The product ##STR14## contains some salt but is used without further purification to prepare azo dyes.

EXAMPLE 2 Diazotization and Coupling

To 50 ml of concentrated H₂ SO₄ is added portionwise with stirring 7.2 g. of dry NaNO₂, allowing the temperature to rise. The nitrosyl sulfuric acid is cooled and 100 ml of 2:5 acid (2 parts propionic:5 parts acetic acid) is added below 15° C. At 0°-5° C., 2-amino-5-[(2-sulfoethyl)thio]-1,3,4-thiadiazole, Na salt (26.4 g, 0.10 m) is added, followed by 100 ml of 2:5 acid. The reaction mixture is stirred for 2 hrs. at 0°-5° C. An aliquot (0.01 m) is added to a solution of (0.01 m) of each of the following couplers in 25 ml of 2:5 acid, at 0°-5° C. After allowing to stand for about 30 min., the coupling mixtures are neutralized by adding 50% NaOH solution at less than 25° C.

N-Ethyl-2-methyl-5-acetamidoaniline

N-2-Acetamidoethyl-N-ethyl-m-toluidine

N-2-Carboxamidoethyl-N-ethyl-m-toluidine

N-2-Carboxamidoethyl-2-methoxy-5-methylaniline

N,N-Diethyl-m-acetamidoaniline

N-2-Hydroxyethyl-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline

N-(2-Hydroxyethyl)-2,3-dihydro-3,6-dimethyl-1,4-benzoxazine

N-Benzyl-N-ethyl-m-acetamidoaniline

The coupling mixture was distilled with about 200 ml of water and the dyes were collected by filtration and washed with NaCl solution. Bright orange to bluish red dyes were obtained which had excellent brightness, lightfastness and heat stability.

The following tables give exemplary dyes of the present invention.

                                      TABLE 1                                      __________________________________________________________________________      ##STR15##                                                                     M Z   R                R.sup.6 R.sup.7                                                                             R.sup.8    R.sup.9                         __________________________________________________________________________     Na                                                                               SO.sub.3                                                                           C.sub.2 H.sub.4  H       H    CH.sub.2 CH.sub.3                                                                         CH.sub.2 CH.sub.2 OCOCH.sub                                                    .3                              Na                                                                               SO.sub.3                                                                           C.sub.2 H.sub.4  "       "    "          CH.sub.2 CH.sub.2 CN            Na                                                                               SO.sub.3                                                                           C.sub.2 H.sub.4  "       "    CH.sub.2 CH.sub.2 OCOCH.sub.3                                                             CH.sub.2 CH.sub.2 OCOCH.sub                                                    .3                              Na                                                                               SO.sub.3                                                                           C.sub.2 H.sub.4  "       "    CH.sub.2 CH.sub.2 CN                                                                      CH.sub.2 CH.sub.2 OH            K SO.sub.4                                                                           C.sub.2 H.sub.4  "       "    "           CH.sub.2 CH.sub.2                                                             OCOCH.sub.3                     K SO.sub.4                                                                           C.sub.2 H.sub.4  NHCOCH.sub.3                                                                           CH.sub.3                                                                            H          CH.sub.2 CH.sub.3               K SO.sub.4                                                                           C.sub.2 H.sub.4  "       "    CH.sub.2 CH.sub.3                                                                         CH.sub.2 CH.sub.2 OH            K SO.sub.4                                                                           C.sub.2 H.sub.4  "       "    "                                                                                          ##STR16##                      Na                                                                               SSO.sub.3                                                                          C.sub.2 H.sub.4  "       "    CH.sub.2 CH.sub.2 CN                                                                      CH.sub.2 CH.sub.2 OCOC.sub.                                                    6 H.sub.5                       Na                                                                               SSO.sub.3                                                                          C.sub.2 H.sub.4  "       "    "          CH.sub.2 CH.sub.2 CH.sub.2                                                     CH.sub.3                        Na                                                                               SSO.sub.3                                                                          C.sub.2 H.sub.4  "       "    CH.sub.2 CH.sub.3                                                                         CH.sub.2 C.sub.6 H.sub.5        Na                                                                               SSO.sub.3                                                                          C.sub.2 H.sub.4  "       "    C.sub.6 H.sub.11                                                                           ##STR17##                      K SO.sub.3                                                                            ##STR18##       "       "    "          CH.sub.2 CH.sub.2 OH            Na                                                                               SO.sub.4                                                                           CH.sub.2 CH.sub.2 CH.sub.2                                                                      "       "    "          CH.sub.2 CH.sub.3               Na                                                                               SO.sub.3                                                                            ##STR19##       "       "    CH.sub.2 CH.sub.3                                                                         "                               Na                                                                               SO.sub.3                                                                            ##STR20##       "       "    CH.sub.2 CH.sub.2 OCH.sub.3                                                                ##STR21##                      Na                                                                               SO.sub.3                                                                            ##STR22##       CH.sub.3                                                                               "    CH.sub.2 CH.sub.2 OH                                                                      CH.sub.2 CH.sub.2 OH            Na                                                                               SO.sub.3                                                                            ##STR23##       "       "    "          CH.sub.2 CH.sub.3               K SO.sub.3                                                                           CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                            "       "    CH.sub.2 CH.sub.2 OCOCH.sub.3                                                             CH.sub.2 CH.sub.2 OCOCH.sub                                                    .3                              Na                                                                               SO.sub.3                                                                            ##STR24##       "       "    CH.sub.2 CH.sub.3                                                                          ##STR25##                      Na                                                                               SO.sub.3                                                                            ##STR26##       "       "    "          CH.sub.2 CH.sub.2 CN            Na                                                                               SO.sub.3                                                                            ##STR27##       "       "    "          CH.sub.2 CH.sub.2 Cl            Na                                                                               SO.sub.3                                                                            ##STR28##       "       "    CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2                                            CH.sub.2                                   Na                                                                               SSO.sub.3                                                                          CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                                                            NHCOCH.sub.3                                                                           "    "          CH.sub.2 CH.sub.3               K SO.sub.4                                                                            ##STR29##       "       "    "          CH.sub.2 CH.sub.2 CN            K SO.sub.3                                                                            ##STR30##       "       "    CH.sub.2 CH.sub.2 OCOCH.sub.3                                                             CH.sub.2 CH.sub.2 OCOCH.sub                                                    .3                              K SO.sub.3                                                                            ##STR31##       "       CH.sub.3                                                                            H          CH.sub.2 CH.sub.2 CN            K SO.sub.3                                                                            ##STR32##       "       "    "          CH(CH.sub.3)CH.sub.2                                                           CH.sub.3                        K SO.sub.3                                                                            ##STR33##       H       OCH.sub.3                                                                           H                                                                                          ##STR34##                      K SO.sub.3                                                                            ##STR35##       CH.sub.3                                                                               H    CH.sub.2 CH.sub.3                                                                         CH.sub.2 CH.sub.2 SO.sub.2                                                     NH.sub.2                        K SO.sub.3                                                                            ##STR36##       NHCOCH.sub.3                                                                           "    H                                                                                          ##STR37##                      Na                                                                               SSO.sub.3                                                                          CH.sub.2 CH.sub.2 SO.sub.2 NHCH.sub.2 CH.sub.2                                                  "       "    "          CH.sub.2 CH.sub.2 OCH.sub.3     K SO.sub.3                                                                           CH.sub.2 CH(SO.sub.3 K)CH.sub.2                                                                 "       "    "                                                                                          ##STR38##                      K SO.sub.4                                                                            ##STR39##       "       "    "                                                                                          ##STR40##                      Na                                                                               SO.sub.3                                                                           CH.sub.2 CH.sub.2 NHSO.sub.2 CH.sub.2 CH.sub.2                                                  "       "    "                                                                                          ##STR41##                      Na                                                                               SO.sub.3                                                                            ##STR42##       "       "    "          CH(CH.sub.3)CH.sub.2                                                           CH.sub.3                        K SO.sub.3                                                                            ##STR43##       H       CH.sub.3                                                                            "                                                                                          ##STR44##                      K SO.sub.3                                                                            ##STR45##       "       H    "          CH.sub.2 CH.sub.2 CN            K SO.sub.3                                                                            ##STR46##       "       "    CH.sub.3   CH.sub.3                        Na                                                                               SO.sub.3                                                                            ##STR47##       "       "    CH.sub.2 CH.sub.3                                                                         CH.sub.2 CH.sub.3               Na                                                                               SO.sub.3                                                                            ##STR48##       "       "    "          CH.sub.2 C.sub.6 H.sub.5        Na                                                                               SO.sub.4                                                                           CH.sub.2 CH(OSO.sub.3 Na)CH.sub.2                                                               "       "    "          C.sub.6 H.sub.11                Na                                                                               SSO.sub.3                                                                          CH.sub.2 CH(SSO.sub.3 Na)CH.sub.2                                                               "       "    "          CH.sub.2 CH.sub.2 OH            Na                                                                               SO.sub.3                                                                           C.sub.2 H.sub.4  "       "    "          CH.sub.2 CH.sub.2 OCOCH.sub                                                    .3                              K SO.sub.4                                                                           C.sub.2 H.sub.4  "       "    "          CH.sub.2 CH(OH)CH.sub.2                                                        OH                              Na                                                                               SSO.sub.3                                                                          C.sub.2 H.sub.4  "       "    "          CH.sub.2 CH.sub.2 CN            K SO.sub.3                                                                            ##STR49##       "       "    CH.sub.2 CH.sub.3 CN                                                                      "                               Na                                                                               SO.sub.4                                                                           CH.sub.2 CH.sub.2 CH.sub.2                                                                      "       "    "          CH.sub.2 CH.sub.2 OH            Na                                                                               SO.sub.3                                                                            ##STR50##       "       "    "          CH.sub.2 CH.sub.2 OCOCH.sub                                                    .3                              K SO.sub.3                                                                           CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                            "       "    "          CH.sub.2 CH.sub.2 OCOC.sub.                                                    6 H.sub.5                       Na                                                                               SO.sub.3                                                                            ##STR51##       "       "    CH.sub.2 CH.sub.2 OH                                                                      CH.sub.2 CH.sub.2 OH            Na                                                                               SSO.sub.3                                                                          CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                                                            "       "    CH.sub.2 CH.sub.2 OCOCH.sub.3                                                             CH.sub.2 CH.sub.2 OCOCH.sub                                                    .3                              K SO.sub.4                                                                            ##STR52##       "       "    C.sub.2 CH.sub.2 SO.sub.2 CH.sub.2                                             CH.sub.2                                   K SO.sub.3                                                                            ##STR53##       Cl      Cl   H          CH.sub.2 CH.sub.2 CN            K SO.sub.3                                                                            ##STR54##       CH.sub.3                                                                               H    CH.sub.2 CH.sub.3                                                                          ##STR55##                      K SO.sub.3                                                                           CH.sub.2 CH.sub.2 NHCOCH.sub.2                                                                  "       "    "          CH.sub.2 CH.sub.3               Na                                                                               SSO.sub.3                                                                          CH.sub.2 CH.sub.2 SO.sub.2 NHCH.sub.2 CH.sub.2                                                  "       "    "          CH.sub.2 CH.sub.2 OH            K SO.sub.3                                                                           CH.sub.2 CH(SO.sub.3 K)CH.sub.2                                                                 "       "    "          CH.sub.2 CH.sub.2 NHCOOC.su                                                    b.2 H.sub.5                     K SO.sub.4                                                                            ##STR56##       "       "    "          "                               Na                                                                               SO.sub.3                                                                           CH.sub.2 CH.sub.2 NHSO.sub.2 CH.sub.2 CH.sub.2                                                  "       "    CH.sub.2 CH.sub.2 CN                                                                      "                               Na                                                                               SO.sub.3                                                                            ##STR57##       NHCOCH.sub.3                                                                           "    CH.sub.2 CH.sub.3                                                                         CH.sub.2 CH.sub.3               K SO.sub.3                                                                            ##STR58##       "       "    "          CH.sub.2 CH.sub.2 OCOCH.sub                                                    .3                              K SO.sub.3                                                                            ##STR59##       "       "    "          (CH.sub.2 CH.sub.2                                                             O).sub.2 CH.sub.2 CH.sub.3      K SO.sub.3                                                                            ##STR60##       NHCOC.sub.6 H.sub.5                                                                    "    "          CH.sub.2 CH.sub.2 CONH.sub.                                                    2                               Na                                                                               SO.sub.3                                                                            ##STR61##       "       CH.sub.3                                                                            H          CH.sub.2 CH.sub.3               Na                                                                               SO.sub.3                                                                            ##STR62##       NHCOCH.sub.3                                                                           OCH.sub.3                                                                           CH.sub.2 CH.sub.3                                                                         "                               Na                                                                               SO.sub.4                                                                           CH.sub.2 CH(OSO.sub.3 Na)CH.sub.2                                                               "       "    "          CH.sub.2 CH.sub.3 OCOCH.sub                                                    .3                              Na                                                                               SSO.sub.3                                                                          CH.sub.2 CH(SSO.sub.3 Na)CH.sub.2                                                               "       "    "          CH.sub.2 CH(OH)CH.sub.3         Na                                                                               SO.sub.3                                                                           C.sub.2 H.sub.4  "       "    CH.sub.2 CH.sub.2 OH                                                                      CH.sub.2 CH.sub.2 OH            K SO.sub.4                                                                           C.sub.2 H.sub.4  "       "    CH.sub.2 CH.sub.2 OCOCH.sub.3                                                             CH.sub.2 CH.sub.2 OCOCH.sub                                                    .3                              Na                                                                               SSO.sub.3                                                                          C.sub.2 H.sub.4  "       "    CH.sub.2 CH.sub.3                                                                          ##STR63##                      K SO.sub.3                                                                            ##STR64##       "       H    "                                                                                          ##STR65##                      Na                                                                               SO.sub.4                                                                           CH.sub.2 CH.sub.2 CH.sub.2                                                                      "       "    "                                                                                          ##STR66##                      H "   CH.sub.2 CH.sub.2                                                                               "       CH.sub.3                                                                            H                                                                                          ##STR67##                      " "   "                "       "    "                                                                                          ##STR68##                      " "   "                "       "    "                                                                                          ##STR69##                      Na                                                                               SO.sub.3                                                                           "                "       "    "                                                                                          ##STR70##                      H "   "                "       "    "                                                                                          ##STR71##                      Na                                                                               "   "                "       "    "                                                                                          ##STR72##                      " "   "                "       "    "                                                                                          ##STR73##                      " "   "                "       "    "                                                                                          ##STR74##                      " "   "                "       "    "                                                                                          ##STR75##                      " "   "                "       "    "                                                                                          ##STR76##                      " "   "                "       "    "                                                                                          ##STR77##                      " "   "                "       "    "                                                                                          ##STR78##                      " "   "                "       "    "                                                                                          ##STR79##                      " "   "                "       "    "                                                                                          ##STR80##                      " "   "                "       "    "                                                                                          ##STR81##                      " "   "                "       "    "                                                                                          ##STR82##                      " "   "                "       "    "                                                                                          ##STR83##                      " "   "                "       "    "                                                                                          ##STR84##                      __________________________________________________________________________

                                      TABLE II                                     __________________________________________________________________________      ##STR85##                                                                     M Z   R                     R.sup.6, R.sup.10, R.sup.11, R.sup.12,                                         R.sup.16       R.sup.8                             __________________________________________________________________________     Na                                                                               SO.sub.3                                                                           C.sub.2 H.sub.4       2,7-di-CH.sub.3                                                                               C.sub.2 H.sub.4 OH                  Na                                                                               SO.sub.3                                                                           C.sub.2 H.sub.4       2,5-di-CH.sub.38-OCH.sub.3                                                                    CH.sub.2 CH(OH)CH.sub.2 OH          Na                                                                               SO.sub.3                                                                           C.sub.2 H.sub.4       2,2,4,7-tetra-CH.sub.3                                                                        C.sub.2 H.sub.4 CONH.sub.2          Na                                                                               SO.sub.3                                                                           C.sub.2 H.sub.4       2,2,4-tri-CH.sub.3                                                                            C.sub.2 H.sub.4 NHCOCH.sub.3        K SO.sub.4                                                                           C.sub.2 H.sub.4       2-CH.sub.37-NHCOCH.sub.3                                                                      C.sub.2 H.sub.4 CN                  K SO.sub.4                                                                           C.sub.2 H.sub. 4      2,2,4-tri-CH.sub.37-NHCOCH.sub.3                                                              C.sub.2 H.sub.4 Cl                  K SO.sub.4                                                                           C.sub.2 H.sub.4       2,-CH(CH.sub.3).sub.27-NHCOCH.sub.3                                                           C.sub.2 H.sub.4 OOCH.sub.3          K SO.sub.4                                                                           C.sub.2 H.sub.4       7-CH.sub.3     C.sub.2 H.sub.4 OC.sub.2                                                       H.sub.5                             Na                                                                               SSO.sub.3                                                                          C.sub.2 H.sub.4       3-CN7-CH.sub.3 C.sub.2 H.sub.4 CONHC.sub.2                                                    H.sub.5                             Na                                                                               SSO.sub.3                                                                          C.sub.2 H.sub.4       3-CONH.sub.27-CH.sub.3                                                                        C.sub.2 H.sub.4 CONH(C.sub.2                                                   H.sub.5).sub.2                      Na                                                                               SSO.sub.3                                                                          C.sub.2 H.sub.4       3-Cl7-CH.sub.3 C.sub.2 H.sub.4 CONHCH.sub.2                                                   C.sub.6 H.sub.5                     Na                                                                               SSO.sub.3                                                                          C.sub.2 H.sub.4       3-OCH.sub.37-CH.sub.3                                                                         C.sub.2 H.sub.4 OOCOC.sub.2                                                    H.sub.5                             K SO.sub.3                                                                            ##STR86##            2,2,4-di-CH.sub.35,8-di-OCH.sub.3                                                             C.sub.2 H.sub.4 NHCOCHCH.sub.2      Na                                                                               SO.sub.4                                                                           CH.sub.2 CH.sub.2 CH.sub.2                                                                           2,2,4-tri-CH.sub.38-OCH.sub.3                                                                 CH.sub.2 C.sub.6 H.sub.5            Na                                                                               SO.sub.3                                                                            ##STR87##            2-CH.sub.3 7-NHCOCH.sub.3                                                                     C.sub.2 H.sub.4 CONHCH.sub.2                                                   OH                                  Na                                                                               SO.sub.3                                                                            ##STR88##            3-OH7-CH.sub.3 C.sub.3 H.sub.6 NHCONHC.sub.2                                                  H.sub.5                             Na                                                                               SO.sub.3                                                                            ##STR89##            2,7-di-CH.sub.3                                                                               C.sub.2 H.sub.5                     Na                                                                               SO.sub.3                                                                            ##STR90##            2,5-di-CH.sub.38-OCH.sub.3                                                                    C.sub.2 H.sub.4 SO.sub.2                                                       NH.sub.2                            K SO.sub.3                                                                           CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                                 2,2,4,7-tetra-CH.sub.3                                                                        C.sub.2 H.sub.4 SO.sub.2                                                       NHC.sub.2 H.sub.5                   Na                                                                               SO.sub.3                                                                            ##STR91##            2,2,4-tri-CH.sub.3                                                                            C.sub.2 H.sub.4 SCH.sub.3           Na                                                                               SO.sub.3                                                                            ##STR92##            2-CH.sub.37-NHCOCH.sub.3                                                                       ##STR93##                          Na                                                                               SO.sub.3                                                                            ##STR94##            2,2,4-tri-CH.sub.37-NHCOCH.sub.3                                                               ##STR95##                          Na                                                                               SO.sub.3                                                                            ##STR96##            2,-CH(CH.sub.3).sub.27-NHCOCH.sub.3                                                            ##STR97##                          Na                                                                               SSO.sub.3                                                                          CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                                                                 7-CH.sub.3                                                                                     ##STR98##                          K SO.sub.4                                                                            ##STR99##            3-CN7-CH.sub.3                                                                                 ##STR100##                         K SO.sub.3                                                                            ##STR101##           3-CONH.sub.27-CH.sub.3                                                                         ##STR102##                         K SO.sub.3                                                                            ##STR103##           3-Cl7-CH.sub.3                                                                                 ##STR104##                         K SO.sub.3                                                                            ##STR105##           3-OCH.sub.37-CH.sub.3                                                                          ##STR106##                         K SO.sub.3                                                                            ##STR107##           2,2,4-di-CH.sub.35,8-di-OCH.sub.3                                                              ##STR108##                         K SO.sub.3                                                                            ##STR109##           2,2,4-tri-CH.sub.38-OCH.sub.3                                                                  ##STR110##                         K SO.sub.3                                                                           CH.sub.2 CH.sub.2 NHCOCH.sub.2                                                                       2-CH.sub.37-NHCOCH.sub.3                                                                       ##STR111##                         Na                                                                               SSO.sub.3                                                                          CH.sub.2 CH.sub.2 SO.sub.2 NHCH.sub.2 CH.sub.2                                                       3-OH7-CH.sub.3                                                                                 ##STR112##                         K SO.sub.3                                                                           CH.sub.2 CH(SO.sub.3 K)CH.sub.2                                                                      2,7-di-CH.sub.3                                                                                ##STR113##                         K SO.sub.4                                                                            ##STR114##           2,5-di-CH.sub.38-OCH.sub.3                                                                     ##STR115##                         Na                                                                               SO.sub.3                                                                           CH.sub.2 CH.sub.2 NHSO.sub.2 CH.sub.2 CH.sub.2                                                       2,2,4,7-tetra-CH.sub.3                                                                         ##STR116##                         Na                                                                               SO.sub.3                                                                            ##STR117##           2,2,4-tri-CH.sub.3                                                                             ##STR118##                         K SO.sub.3                                                                            ##STR119##           2-CH.sub.37-NHCOCH.sub.3                                                                       ##STR120##                         K SO.sub.3                                                                            ##STR121##           2,2,4-tri-CH.sub.37-NHCOCH.sub.3                                                               ##STR122##                         K SO.sub.3                                                                            ##STR123##           2,-CH(CH.sub.3).sub.27-NHCOCH.sub.3                                                            ##STR124##                         Na                                                                               SO.sub.3                                                                            ##STR125##           7-CH.sub.3                                                                                     ##STR126##                         Na                                                                               SO.sub.3                                                                            ##STR127##           3-CN7-CH.sub.3 C.sub.2 H.sub.4 OH                  Na                                                                               SO.sub.4                                                                           CH.sub.2 CH(OSO.sub.3 Na)CH.sub.2                                                                    3-CONH.sub.27-CH.sub.3                                                                         ##STR128##                         Na                                                                               SSO.sub.3                                                                          CH.sub.2 CH(SSO.sub.3 Na)CH.sub.2                                                                    2,2,4,7-tetra-CH.sub.3                                                                         ##STR129##                         Na                                                                               SO.sub.3                                                                           C.sub.2 H.sub.4       2,2,4,7-tetra-CH.sub.3                                                                         ##STR130##                         __________________________________________________________________________

                                      TABLE III                                    __________________________________________________________________________      ##STR131##                                                                    M Z      R                  R.sup.6, R.sup.10                                                                           R.sup.8                               __________________________________________________________________________     Na                                                                               SO.sub.3                                                                           C.sub.2 H.sub.4      3,6-di-CH.sub.3                                                                           C.sub.2 H.sub.4 OH                       Na                                                                               SO.sub.3                                                                           C.sub.2 H.sub.4      3-CH.sub.3 CH.sub.2 CH(OH)CH.sub.2 OH               Na                                                                               SO.sub.3                                                                           C.sub.2 H.sub.4      3-CH.sub.36-NHCOCH.sub.3                                                                  C.sub.2 H.sub.4 CONH.sub.2               Na                                                                               SO.sub.3                                                                           C.sub.2 H.sub.4      6-NHCOCH.sub.3                                                                            C.sub.2 H.sub.4 NHCOCH.sub.3             K SO.sub.4                                                                           C.sub.2 H.sub.4      3,6-di-CH.sub.3                                                                           C.sub.2 H.sub.4 CN                       K SO.sub.4                                                                           C.sub.2 H.sub.4      3-CH.sub.3 C.sub.2 H.sub.4 Cl                       K SO.sub.4                                                                           C.sub. 2 H.sub.4     3-CH.sub.36-NHCOCH.sub.3                                                                  C.sub.2 H.sub.4 OOCC.sub.2 H.sub.5       K SO.sub.4                                                                           C.sub.2 H.sub.4      6-NHCOCH.sub.3                                                                            C.sub.2 H.sub.4 OC.sub.2 H.sub.5         Na                                                                               SSO.sub.3                                                                          C.sub.2 H.sub.4      3,6-di-CH.sub.3                                                                           C.sub.2 H.sub.4 CONHC.sub.2                                                    H.sub.5                                  Na                                                                               SSO.sub.3                                                                          C.sub.2 H.sub.4      3-CH.sub.3 C.sub.2 H.sub.4 CONH(C.sub.2                                                   H.sub.5).sub.2                           Na                                                                               SSO.sub.3                                                                          C.sub.2 H.sub.4      3-CH.sub.36-NHCOCH.sub.3                                                                  C.sub.2 H.sub.4 CONHCH.sub.2                                                   C.sub.6 H.sub.5                          Na                                                                               SSO.sub.3                                                                          C.sub.2 H.sub.4      6-NHCOCH.sub.3                                                                            C.sub.2 H.sub.4 OOCOC.sub.2                                                    H.sub.5                                  K SO.sub.3                                                                            ##STR132##          3,6-di-CH.sub.3                                                                           C.sub.2 H.sub.4 NHCOCHCH.sub.2           Na                                                                               SO.sub.4                                                                           CH.sub.2 CH.sub.2 CH.sub.2                                                                          3-CH.sub.3 CH.sub.2 C.sub.6 H.sub.5                 Na                                                                               SO.sub.3                                                                            ##STR133##          3-CH.sub.36-NHCOCH.sub.3                                                                  C.sub.2 H.sub.4 CONHCH.sub.2 OH          Na                                                                               SO.sub.3                                                                            ##STR134##          6-NHCOCH.sub.3                                                                            C.sub.3 H.sub.6 NHCONHC.sub.2                                                  H.sub.5                                  Na                                                                               SO.sub.3                                                                            ##STR135##          3,6-di-CH.sub.3                                                                           C.sub.2 H.sub.5                          Na                                                                               SO.sub.3                                                                            ##STR136##          3-CH.sub.3 C.sub.2 H.sub.4 SO.sub.2 NH.sub.2        K SO.sub.3                                                                           CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                                3-CH.sub.36-NHCOCH.sub.3                                                                  C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                             H.sub.5                                  Na                                                                               SO.sub.3                                                                            ##STR137##          6-NHCOCH.sub.3                                                                            C.sub.2 H.sub.4 SCH.sub.3                Na                                                                               SO.sub.3                                                                            ##STR138##          3,6-di-CH.sub.3                                                                            ##STR139##                              Na                                                                               SO.sub.3                                                                            ##STR140##          3-CH.sub.3                                                                                 ##STR141##                              Na                                                                               SO.sub.3                                                                            ##STR142##          3-CH.sub.36-NHCOCH.sub.3                                                                   ##STR143##                              Na                                                                               SSO.sub.3                                                                          CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                                                                6-NHCOCH.sub.3                                                                             ##STR144##                              K SO.sub.4                                                                            ##STR145##          3,6-di-CH.sub.3                                                                            ##STR146##                              K SO.sub.3                                                                            ##STR147##          3-CH.sub.3                                                                                 ##STR148##                              K SO.sub.3                                                                            ##STR149##          3-CH.sub.36-NHCOCH.sub.3                                                                   ##STR150##                              K SO.sub.3                                                                            ##STR151##          6-NHCOCH.sub.3                                                                             ##STR152##                              K SO.sub.3                                                                            ##STR153##          3,6-di-CH.sub.3                                                                            ##STR154##                              K SO.sub.3                                                                            ##STR155##          3-CH.sub.3                                                                                 ##STR156##                              K SO.sub.3                                                                           CH.sub.2 CH.sub.2 NHCOCH.sub.2                                                                      3-CH.sub.36-NHCOCH.sub.3                                                                   ##STR157##                              Na                                                                               SSO.sub.3                                                                          CH.sub.2 CH.sub.2 SO.sub.2 NHCH.sub.2 CH.sub.2                                                      6-NHCOCH.sub.3                                                                             ##STR158##                              K SO.sub.3                                                                           CH.sub.2 CH(SO.sub.3 K)CH.sub.2                                                                     3,6-di-CH.sub.3                                                                            ##STR159##                              K SO.sub.4                                                                            ##STR160##          3-CH.sub.3                                                                                 ##STR161##                              Na                                                                               SO.sub.3                                                                           CH.sub.2 CH.sub.2 NHSO.sub.2 CH.sub.2 CH.sub.2                                                      3-CH.sub.36-NHCOCH.sub.3                                                                   ##STR162##                              Na                                                                               SO.sub.3                                                                            ##STR163##          6-NHCOCH.sub.3                                                                             ##STR164##                              K SO.sub.3                                                                            ##STR165##          3,6-di-CH.sub.3                                                                            ##STR166##                              K SO.sub.3                                                                            ##STR167##          3-CH.sub.3                                                                                 ##STR168##                              K SO.sub.3                                                                            ##STR169##          3-CH.sub.36-NHCOCH.sub.3                                                                   ##STR170##                              Na                                                                               SO.sub.3                                                                            ##STR171##          6-NHCOCH.sub.3                                                                             ##STR172##                              Na                                                                               SO.sub.3                                                                            ##STR173##          3,6-di-CH.sub.3                                                                           C.sub.2 H.sub.4 OH                       Na                                                                               SO.sub.4                                                                           CH.sub.2 CH(OSO.sub.3 Na)CH.sub.2                                                                   3-CH.sub.3                                                                                 ##STR174##                              Na                                                                               SSO.sub.3                                                                          CH.sub.2 CH(SSO.sub.3 Na)CH.sub.2                                                                   3,6-di-CH.sub.3                                                                            ##STR175##                              Na                                                                               SO.sub.3                                                                           C.sub.2 H.sub.4      3,6-di-CH.sub.3                                                                            ##STR176##                              __________________________________________________________________________

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the inventon. 

We claim:
 1. A compound having the formula ##STR177## in which R is ##STR178## an alkali metal or ammonium; and A is selected from coupler moieties of the formulae ##STR179## wherein R⁶ and R⁷ are each selected from hydrogen, fluorine, chlorine, bromine, lower alkyl, cycloalkyl, lower alkoxy, phenoxy, lower alkylthio, arylthio, and --NH--X--R¹³ in which X is --CO--, --COO--, or --SO₂ -- and R¹³ is selected from aryl, cycloalkyl, lower alkyl and lower alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, lower alkylsulfonyl, lower alkylthio, lower alkanoyloxy, and lower alkoxy, and when X is --CO--, R¹³ is also selected from hydrogen, amino, lower alkylamino, lower alkylcarbamoyl, lower dialkylamino, arylamino, and furyl;R⁸ and R⁹ are selected from hydrogen; cycloalkyl; cycloalkyl substituted with one or two groups selected from lower alkyl, --OH, lower alkoxy, halogen and hydroxy substituted lower alkyl; phenyl or phenyl substituted with lower alkyl, lowr alkoxy, halogen, lower alkanoylamino, cyano or lower alkoxycarbonyl; straight or branched lower alkenyl; straight or branched alkyl or 1-8 carbons and such alkyl substituted with the following: hydroxy; halogen; cyano; succinimido; glutarimido; phthalimidino; 2-pyrrolidono; cyclohexyl; phenyl or phenyl substituted with 1-3 of lower alkyl, halogen, cyano, sulfamoyl, OH, OR¹³, OXR¹³, SR¹³, NHXR¹³, SO₂ NHR¹³, O(CH₂)_(n) XR¹³, O(CH₂)_(n) OR¹³, or ##STR180## where n is 1-6; lower alkanoylamino; sulfamoyl, lower alkylsulfamoyl; vinylsulfonyl; acrylamido; phthalimidinyl; benzoylsulfonicimidyl; lower alkylsulfonamido; phenylsulfonamido; lower alkoxycarbonylamino; lower alkylcarbamoyloxy; lower alkoxycarbonyl; lower alkoxycarbonyloxy; ##STR181## wherein Y is --NH--, --NH--lower alkyl--, --O--, --S--, or --CH₂ O--; --S--R¹⁴ wherein R¹⁴ is lower alkyl, phenyl, phenyl substituted with halogen, lower alkyl, lower alkoxy, lower alkanoylamino, cyano, or lower alkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, or ##STR182## --SO₂ R¹³ ; --COOR¹³ ; --OXR¹³ ; --NH--X--R¹³ ; --X--R¹³ ; --OCO--R¹³ ; --CONR¹⁵ R¹⁵ ; --SO₂ NR¹⁵ R¹⁵ ; wherein R¹³ and X are as defined above and each R¹⁵ is selected from H and R¹³ ; lower alkoxy, lower alkoxy substituted with hydroxy, cyano, lower alkanoyloxy, or lower alkoxy; phenoxy; phenoxy substituted with one or more of lower alkyl, lower alkoxy or halogen; or R⁸ and R⁹ combined form pentamethylene, ethyleneoxyethylene or ethylenesulfonylethylene; R¹⁰, R¹¹, and R¹² are each selected from hydrogen and lower alkyl; and R¹⁶ is selected from --OH, --Cl, --CONH₂, --CONH--lower alkyl, lower alkoxy, phenoxy, --SR¹⁴, and --OXR¹³ wherein R¹³ and R¹⁴ are as defined above.
 2. A compound according to claim 1 whereinA is a coupler moiety of one of the formulae ##STR183## wherein R⁶ is lower alkyl, lower alkoxy, lower alkanoylamino, or lower alkoxycarbonylamino;R⁷ is hydrogen, lower alkyl, or lower alkoxy; R⁸ and R⁹ are the same or different and selected from hydrogen, lower alkyl, and lower akyl substituted with hydroxy, alkoxy, alkoxyalkoxy, hydroxyalkoxy, carbamoyl, lower alkylcarbamoyl, lower alkanoylamino, sulfamoyl, lower alkylsulfamoyl, phenyl, o-chlorophenyl, p-alkoxycarbonylphenyl, p-benzyloxyphenyl, cyclohexyl, 2-pyrrolidono, phthalimido, succinimido, cyano, phenoxy, alkylsulfonyl, phthalimidinyl, benzoylsulfonicimidyl, triazolylthio, lower alkylsulfonamido, --SO₂ NH₂, --SO₂ NHR, phenylsulfonamido, lower alkoxycarbonylamino, lower alkylcarbamoyloxy, lower alkoxycarbonyl, lower alkoxycarbonyloxy, 2-benzothiazolylthio, ##STR184## R¹⁰ and R¹² are each hydrogen or lower alkyl.
 3. An azo compound according to claim 1 having the formula ##STR185##
 4. An azo compound according to claim 1 having the formula ##STR186##
 5. An azo compound according to claim 1 having the formula ##STR187##
 6. An azo compound according to claim 1 having the formula ##STR188##
 7. An azo compound according to claim 1 having the formula ##STR189##
 8. An azo compound according to claim 1 having the formula ##STR190##
 9. An azo compound according to claim 1 having the formula ##STR191##
 10. An azo compound according to claim 1 having the formula ##STR192##
 11. An azo compound according to claim 1 having the formula ##STR193## 